JPS60219214A - Optionally porous foamable composition and use - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application] The present invention comprises a combination of a polyol, a cyanuric acid derivative and a phosphorous-containing polyhydroxyl compound as part of the formulation, and has rigid properties, optionally porous, Foaming compositions based on polyurethane (Intumeac
ent composltlons).

[Prior art and problems to be solved by the present invention]
An intumescent composition is a material that foams when exposed to fire or heat, and by behaving as such, forms an insulating, fire-retardant foam that protects the area behind it from the effects of fire. It is understood that Foamable compositions are known in the form of lacquers, coatings, mortars and cements.

A good foaming composition should not only at least double its volume when exposed to flame, but also be unaffected by water. More specifically, if these properties can be combined with the absence of no-rodane and a low density or foam structure, i.e. a certain insulating effect in the absence of stress, as well as hardness and optionally toughness. If so, the foamable composition would be of commercial interest.

Solid or foamed rigid foam compositions with high dimensional stability can be widely used in the field of fire protection in the form of semi-finished products such as boards, moldings, profiles, coatings, granules or light fillers. was completed.

The use of melamine in the production of flexible foams using substantially linear polyols, preferably polyether polyols, is known in principle (German Patent Application No. 21/3!;' No. I). Although such foams are substantially non-flammable and do not completely burn out when exposed to flame, the extent to which they do not expand in volume when exposed to flame and form a fire-retardant foam is limited by any intumescent composition. It does not have the properties of a thing.

According to German Patent Application No. 30.23.2/7, phosphorus- and rodan-free flame-retardant sealing materials can be produced using branched polyesters containing hydroxyl groups. Both such sealants are non-foaming, ie, do not form a foam when exposed to flame.

German Patent Application No. 3023307 defines X polyinsyanate as: 1. an aliphatic, cycloaliphatic, aromatic, ararifatic or heterocyclic primary or primary monoamine, optionally containing hydroxyl groups; and/or phosphorus-containing condensation products containing at least two hydroxyl groups obtained by condensation of polyamines, carbinyl compounds and dialkyl phosphites, optionally followed by alkoxylation, and 3. aromatic hydroxyl carbic acids or salts thereof. and Hiroshi describes optionally foamed foamable compositions obtained by reacting optionally water and/or other organic compounds containing isocyanate-reactive hydrogen atoms.

According to this West German Patent Application, polyesters containing hydroxyl groups and melamines can also be used, but these polyesters are not otherwise branched, i.e. the polyfunctional polyesters used according to the invention. Rather, it is a linear polyester. In this case, hard products are always obtained, the brittleness of which is often a hindrance to their easy use.

According to German Patent Application No. 30 11 173/, phosphorus-containing condensation products containing at least one hydroxyl group, polyesters and cyanuric acid (derivatives) and Pa optionally water and optionally incyanate reactive Optionally foamed plastic elastic foamable compositions are obtained by reacting a mixture of other organic compounds containing hydrogen atoms with polyisocyanates.

[Means for solving problems]

Surprisingly, West German patent application publication specification letter 301
The cyanuric acid derivative preferably used according to No. 1-1731, namely melamine, can not only be replaced by melamine phosphate, but also by increasing the amount of incyanate used and at the same time decreasing the amount of KyN-liol. It has now been discovered that strong, rigid foams with excellent foaming properties can be obtained.

A completely unexpected benefit of these new foamable compositions is that they do not melt before being exposed to a flame and foaming, i.e., the foamed material does not melt due to critical conditions of thermal stress. It consists in the fact that it comes into contact with an actual flame.

Therefore, 1 the present invention provides 33 to 0 parts by weight of /,yff reisocyanate to
condensation of aliphatic, cycloaliphatic, aromatic, arariphatic or heterocyclic primary or primary monoamines and/or polyamines, carboxylic compounds and dialkyl phosphites, optionally containing hydroxyl groups; Optionally followed by Al; a phosphorus-containing condensation product containing at least one hydroxyl group obtained by xylation! θ
~75M view%, 3, C2-C,. Polycarbic acid is divided into the following three groups.

i.e. a) contains more than one hydroxyl group, and 20
a hydroxyl compound having a molecular weight of θ or less; b) a hydroxyl compound containing 3 hydroxyl groups and having a molecular weight of /30 or less; c) a hydroxyl compound containing 2 hydroxyl groups and having a molecular weight of /10 or less Compound.

by reacting with at least two polyols selected from two different groups of: OH
hydroxyl-containing polyester having a number/1 JtO to 3θO, a weight factor of 2 to 30, where seven of the above polyols are a)
The average 0H1j! must belong to the group and was obtained by adding an alkylene oxide, of which 30 to 10% loOM amount consists of ethylene oxide, to a low molecular weight starting substance! Optionally use an I ether with i/, 20-400, 25-75% by weight of melamine and/l or melamine derivative and 0~! It is obtained by reacting with 100 parts by weight of a mixture consisting of II. The present invention relates to optionally foamed foamable compositions.

The polyisocyanates used are those of the type obtained by phosgenation of aniline-formaldehyde condensates, those of the type containing condensates corresponding to the formula below as condensation products containing at least two hydroxyl groups? Reincyanate.

(RO)2PO-CH2-N=(CHX-needle ■-0H)
,.

(In the formula, R represents a C1-C8 alkyl group or a c, -c8 hydroxyalkyl group, and X represents a hydrogenated methyl group) and a type of polyisocyanate containing melamine phosphate as a melamine derivative. Foamable compositions are particularly selected.

The invention also relates to foamable solid or porous cavity fillers, lining-insulators, structures, structural components, semi-finished products,
This new foamable material can be used to produce foamable molded articles as granules, powders, void light fillers and coatings, either by reaction in the mold or later by the formation of a fully reacted reaction mixture. Relating to using the composition.

According to the invention, foamable compositions which are clearly stiff and optionally foamed are obtained. The preforms obtained from the molded rigid or tough rigid foam compositions obtained according to the invention are particularly easy to process by sawing or cutting, as well as by cable cutting. This foamable composition may be of particular commercial interest since it can also be used to encase tubes and tubes, and its performance is not affected by vibrations in the application field. Since the semi-finished products obtained from this foamable composition can be thermoplastically molded at temperatures in the range of about 60 to 0°C, the fact that the composition has excellent water resistance is another important consideration. There are two commercially interesting advantages.

The foamable compositions obtained according to the invention are substantially non-flammable even in the absence of halogen compounds. When exposed to flame, its composition up to 10 times the volume of the animal,
or even more, and by acting as such forms a flame-retardant foam that protects the surrounding areas of the composition from coming into contact with flame. This composition does not melt or flow when heated.

The composition can be thermoplastically processed near (ie, below) its foaming temperature. If the temperature is controlled appropriately during thermoplastic processing (e.g. pressing, deep drawing) to form a molded product, the resulting molded product will have an expandable property. Or it can be solid. Its thermoplastic strength under certain processing conditions is 1k.

It can also be used to change the shape of molded articles, for example panels of foamed material, for example for separating or welding them into other parts, or for stamping and permanent deformation.

This new foamable material can be manufactured either continuously or batchwise.

This foamable material is prepared by mixing each component or a premix of each component on site and then mechanically or manually without applying pressure or under pressure, e.g. The reaction mixture is injected or squirted into an uncontained mold, causing the foamable material to foam and harden within the mold. The process mixture according to the invention is first processed into semi-finished products, for example foams, profiles or coatings, and these semi-finished products are then subjected to the necessary processes 1, for example cutting, thermoforming, granulation, grinding or mixing, shaping or bonding. Further processing is also possible.

The reaction mixture is treated with foamed or solid inorganic or rri
Organic additives, such as polystyrene 7 ohm, polyurethane foam, phenolic resin, amino resin or gravel or expanded clay, urea resin or phenolic resin foam, foamed glass, aluminum fiber, wood, mineral fiber, pumice By mixing with the like, it is also possible to obtain a special effervescent material. The foamable compositions of the invention can also be used for the production of molded articles reinforced with fibers or wires, or with metal plates, textiles, strands of organic or inorganic materials or non-woven fabrics, and for the production of multilayer materials and sand-like materials. It can also be used as an ingredient.

The foamable compositions of the present invention may also include other organic or inorganic foamable materials such as water-containing silicates, expandable graphite, phenolic resins, urea resins, melamine resins.

It can also be mixed with x, H xy resin, polyurethane resin, etc.

Suitable fillers that can be used individually or in combination are:
Especially aluminum oxide hydrate, chalk.

Solid or hollow pieces of kaolin-, glass- and silicate-containing materials, such as so-called microballoons. Aluminum oxide hydrates are also preferred as solid beads, since these light fillers can be dehydrated. .

Mineral sI! Other textile fibers that can be used in addition to kasuri, glass fibers, carbon fibers or organic fibers include light fillers or foams in the form of granules, powders, small rods, ribbons, various microcrystals, beads or hollows. It is a bead-shaped light filling.

According to the invention, from 100°C to 700°C, preferably /2
It is also possible to use dehydrating or ammonia-releasing photocondensations that use up heat 11 by decomposition or water release or evaporation at temperatures in the range θ°C to 700°C.

Such optical fillers are described, for example, in West German patent application No. Le
Alkali silicates, zeolites and other hydrated phosphates, silicates, borosilicates or borates, aluminum oxide hydrates, cyanuric acid conductors and the like as described in No. A, 22/&. compounds, phenolic resins,
Melamine resins and urea-formaldehyde resins, expandable graphite and mica, vermiculite and norolite, minerals containing water of crystallization, such as aluminohydrocalcite, altinite, doutsonite, ettringite, hydrocalumite, noidolite, etc. Nate (hydr
oganate), hydromagnetite, hydrotalcite, nesquehonite, scarbroite (5carbr
olte), thaumasite and wermlandite, but of particular interest are aluminum hydroxide and hydrated aluminum oxide or hydric alumina.

Anhydrous zeolites are suitable photofillers for binding water in the reaction mixture, the amount used being governed by the requirements.

B The starting components for producing the foamable composition of the present invention are, for example, those produced by Justus Llsblgs Annalend.
er Chemie ), ,! r otsu-2 page 7j~
On page 136, B's Fken (W, 5lsfken)
aliphatic, cycloaliphatic, araliphatic, of the type mentioned by )
Aromatic and heterocyclic polyisocyanates, such as polyisocyanates having the general formula:

Q(NGO) (wherein n=!~g, preferably -, and Q is an aliphatic hydrocarbon group containing 2 to 7 g, preferably 4 to 70 carbon atoms, q~/j) , an alicyclic hydrocarbon group containing preferably 6 to IO carbon atoms, an aromatic hydrocarbon group containing 6 to /!, preferably 6 to /3 carbon atoms, or g to /j , preferably araliphatic hydrocarbon radicals containing from g to 73 carbon atoms) such as ethylene diisocyanate, /, coutetramethylene diisocyanate, /, o-hexamethylene diisocyanate, /, /, 2-dodecane diisocyanate , cyclobutane-/,3-diincyanate.

Cyclohexane-/, 3- and -/, <4-diisocyanates and mixtures of these isomers, /-incyanato-3,3,j-) Rimeteru! - incyanatomethylcyclohexane (West German patent application publication specification letter 12
0.27gj, U.S. Patent No. 3g0//ri No.0 specification value)
,! , Doug and 2. o-hexahydrotolylene diisocyanate, and mixtures of these x-isomers, hexahydro-/, 3-x and 7- or -/l kufenylene diisocyanate, -, -, 4-hydro, ', 4' - and/or -g, <z-diphenylmethane diisocyanate, , 2.4- and! , O-tolylene diisocyanate and mixtures of these isomers, diphenylmethane-! , 1- and/or 1-g, hiro'-diisocyanate, 7-tyrene-/, j-diisocyanate.

According to Kinoto i1+'JK, for example, triphenylmethane-
II, II', II/-triisocyanate, by phosgenation of the aniline-pormaldehyde condensate, and for example British Patent Specification Letter g7, ≠3
No. 0 and No. 4 are the molded phenyl-methylene I reinocyanates described in No. Otsu No. 7/.

U.S. Patent No. 3. m- and p-incyanatophenylsulfonyl incyanate according to the Ministry of Specification No. 60
For example, 4-chlorinated aryl incyanates of the type described in West German Patent Application Publication No. 1/j7 O/ (U.S. Pat. No. 3277/3♂ Specification 1), West German Patent Application No. 10, 2007 No. J Measurement (U.S. Patent No. 3/!;
7/l.

Saimei Device) and West German Patent Application Publication Specification No. 1, 2J
-θg 4too issue, No. 2!376O! No. and No. 2
63.23t0, U.S. Patent No. 311-92
Norbornane diincyanate according to specification No. 330,
For example, British Patent No. 9 Hari 90, Belgian Patent No. 7, No. 26, and Dutch Patent Application No. 71.
02. ! ;, polyinsyanates containing allophanate groups of the type described in US Pat. No. 300/973, West German Patent Specification Letter 10.
2.27g, No. 12.2.20t, No. 7 Oyobi No. 1
OJ 735;No.
(7'I O'A I No.K Polyinsyanates containing incyanurate groups of the type described, e.g. Belgian Patent No. 7J-,2,2z) Saimei apparatus or U.S. Pat. and polyisocyanates containing urethane groups of the type described in US Pat. Book No. 3/, 24tzOj No. 320/3
7.2 and 37.2≠603 and containing biuret groups of the type described in British Patent No. Kg 050. Liisocyanate 2 e.g. U.S. Patent No. 36
A polyincyanate produced by a telomolization reaction of the type described in Suio No.

For example, British Patent EAMl Letter No. 2 Gua≠ and No. 7
07.29. polyisocyanates containing ester groups of the type described in Saimei Apparatus in U.S. Pat. No. 336,771.3 a and West German Patent No. 1.2J/6g, according to West German Patent No. 107.23gj The reaction product of the aforementioned incyanate and acetal and US Pat. No. 341! It is also possible to use polyisocyanates containing polymerized fatty acid esters according to '♂r No. 3 specification.

It is also possible to use distillation residues containing incyanate groups, collected in the commercial production of incyanates, optionally in solution form in one or more of the aforementioned polyisocyanates. Mixtures of the aforementioned polyisocyanates can also be used.

In general, polyisocyanates that are easily available in the West and East, for example! , Goo and! Particularly preferred is the use of O-trilene ynonanate and mixtures of these isomers ("TDl"), but also of the type obtained by phoscination of aniline-formaldehyde composites. Riphenyl Irimethylenepa? Liisocyanate (crude g
MDIJ) Polyinsyanates (“modified polyisocyanates”) which contain cardidiimide groups, urethane groups, allophanate groups, incyanurate groups, urinary groups or biuret groups, especially! , 4'- and/or! , Otolylene diisocyanate or 4t'-
and/or! Particularly preferred are modified polyisocyanates of the type derived from lysinenylmethane diisocyanate.

! 0 For example, aliphatic, optionally containing a hydroxyl group.

B "Types obtainable by condensation of cyclic, aromatic, arariphatic or heterocyclic primary or primary monoamines and/or amines with dialkyl phosphites and optionally subsequent alkoxylation. Phosphorus-containing condensation products containing at least one hydroxyl group, such as those described for example in West German Patent No. 1 iti3o, 2.2, US Pat. Letter 1 g
037 Gutsu issue and 1'/, 2g! It is known per se from No. Otsuj.

According to the invention, the phosphorus-containing condensation product containing at least two hydroxyl groups is a condensation product of the formula:

(RO)2RO-CH2-N=(CHX-CHX-OH
) In the formula 2, R is a C1-C6 alkyl group or C, -08
represents a hydroxyalkyl group, preferably an ethyl group or a hydroxylthyl group, and X-is hydrogen or a methyl group, preferably hydrogen;
Aliphatic, cycloaliphatic, arariphatic and aromatic C
A hydroxyl-containing polyester having a number of /jO to 3000H obtained by reacting a 2-CTo polycarboxylic acid with at least two polyols selected from one of the following three groups:

a) contains more than 3 hydroxyl groups and 2
00; b) hydroxyl compounds containing 3 hydroxyl groups and having a molecular weight of 5 and /jO; c) containing 2 hydroxyl groups and having a molecular weight of up to /10. hydroxyl compound, and / of the above s91Jol
Rare must belong to group a).

Suitable polycarboxylic acids are the carboxylic acids known per se, in addition to benzenedicarboxylic acids.

Preference is given to aliphatic tericarboxylic acids containing 3 to IO carbon atoms.

Examples of benzenedicarboxylic acids are fumeric acid and terephthalic acid. The aliphatic polycarboxylic acids used are, in particular,
Aliphatic polycarboxylic acids containing from 3 to g carbon atoms, such as citric acid, oxalic acid, maleic acid and fumaric acid, succinic acid, and adipic acid are readily available;
preferable.

Among the hydroxyl compounds in the &) group, for example, mannitol, sorbitol, xylitol, formitol, ie sugar polyols can also be used, and luca and intererythol are preferred.

Among the hydroxyl compounds belonging to group b), for example trimethylolpropane or triethanolamine can also be used, but glycerol is preferred.

Among the hydroxyl compounds belonging to group C), besides propylene glycol, pure butanediol or neopentyl glycol, ethylene glycol is preferred.

For purposes of the present invention, highly branched polyesters of adipic acid, pentaerythritol, glycerol and ethylene glycol are particularly preferred.

These polyesters have jOO~za0 at 73'C.
t00~J' 0 at 75°C with a viscosity of 0 cP
A viscosity of 0.00 cP is preferred. The acid number must be less than 70, preferably 0 or less. The molecular weight is 300-
．． 20θ0, preferably Ooo~/! 0θ range, and the OH number is /10 to 300, preferably /70 to
．． It is in the range of 2.20.

According to the present invention, a polyether having an average OH number of 7.20 to 300f is obtained by adding an alkylene oxide consisting of ethylene oxide to a low molecular weight starting substance of Tzelevitinoff activity, and has an average OH number of 7.20 to 300f. used. - Great sensuality and 2oo-<
Particularly preferred are polyethers with an OH of 92.

In the context of the present invention, "having a functionality greater than 2" means that difunctional polyethers are also present in the mixture with trifunctional and/or higher functionality polyethers. A functionality of 2.3 to 4t is preferred.

Although, according to the invention, ethylene oxide adducts are preferably used as polyethers, in principle it is also possible to replace up to about jOit parts of the adducted ethylene oxide with propylene oxide or other alkylene oxides. However, the foaming and/or combustion behavior of the foamable composition can then be expected to deteriorate, as a result of the use of polyethers prepared using alkylene oxides such as propylene oxide in addition to ethylene oxide. If only ethylene oxide is used, this is not preferable.

Epichlorohydrin can also be used, although this presents the disadvantage of the presence of halogen.

Polyethers are produced by methods known to experts in the field of 4-liether chemistry.

Suitable low molecular weight starting molecules are the compounds known per se for the preparation of polyethers, such as water, ethylene glycol, propylene glycol, butanediol, trimethylolpropylene, glycerol.

Triethanolamine, -entaerythritol-/l/.

Ethylenediamine, tolylenediamine, various sugars and their hydrogenation products, formose and formitol, aniline, ]? Lipolykylene, gallamine, benzidine and its hydrogenation products.

Aniline-formaldehyde condensate and its hydrogenation product. Aliphatic and aromatic polycarpinic acids are also suitable starter steels, as are amino alcohols such as amino acids or ethanolamine.

Halogen containing starting materials such as brominated alcohols such as bis-bromomethylpropanediol can also be used.

Although polyesters and/or polyethers of various structures must account for up to 20% by weight of the total amount of IF +7ol, these compounds can also be used in principle.

≠ Melamine and /′−! or derivatives thereof, i.e. compounds which can further be interpreted as cyanuric acid and cyanuric acid or isocyanuric acid derivatives. Such compounds are, for example, cyanamide, dicyanamide.

Nocyanocyamide, guanidino and its salts, biguanides, melamine cyanurates, cyanurates and cyanuric acid esters and amides, with melamine being particularly preferred because of its easy availability.

Condensation products of melamine, obtained for example by heat treatment or reaction with formaldehyde, can also be used, but melamine is the sharpest compound, ie! I, O-triamino-
Preferably it is used in the form of the 8-triazone.

A melamine derivative of particular interest is oxalic acid.

・Location acetic acid, HBr, sulfuric acid, molybdic acid,
Salts with organic and inorganic acids such as boric acid, but especially with phosphoric acid and polyphosphoric acid, ie derivatives of the melamine phosphate type.

The derivatives of the melamine phosphate type are preferably used in a proportion of 1 mol of melamine and 0.0/-2.5 mol, preferably 0.0/-2.5 mol.
! ~/, θ moles of orthophosphoric acid, but other phosphoric acids, such as metaphosphoric acid, pyrophosphoric acid or polyphosphoric acid or phosphoric acids with other valence stages of phosphorus, are also taken into account. I can do it. The phosphate is produced, for example, by reacting melamine with orthophosphoric acid in an aqueous suspension at 10 DEG to 7.20 DEG C., cooling, PJ, and drying. Instead of melamine phosphate, which has a low phosphate content, it is possible to use melamine, a mixture with melamine phos-7ate, which has a high phosphate content.

However, in general for BAK, "phosphates of the melamine phosphate type" are soluble in water (in the form of a saturated solution at room temperature) to a lesser extent, preferably less than %/wt. , compounds which can be considered as cyanuric acid conductors, such as cyanamide, dicyanamide, hydrazonocarbonamide, dicyanodiamine, guanidine and its salts, biguanides, urazole, urazole cyanurate, melamine cyanurate, cyanurate and Includes phosphate salts optionally formed by the "addition of phosphoric acid to melamine, which is preferred for its ready availability to cyanuric acid esters and amides (91%)."

j　Water optionally.

It has been found that the normal stoichiometry in conventional polyurethane chemistry is not a characteristic of the favorable properties of the new foamable compositions, particularly the foamable foams. component! , 3.
17-and! are mixed irrespective of the required stoichiometry in isocyanate chemistry, and the mixtures thus obtained are tested in simple preliminary tests to determine experimentally the optimum activity required. Reacts with various polyinsyanates within the range suitable for this invention.

The individual components in the reaction mixture to be reacted with the polyincyanate, 2, 3. The approximate amounts thus determined for the group and optionally the evening sum to 700%;
And for the phosphorus-containing condensation product (,2) containing at least one hydroxyl group, the weight ratio is 20-75 yen, preferably 30-! O Weight section: -Polyester (3
) for 2-3θ weight factor, preferably t-1t weight factor: - For melamine conductor (4t)! j to 75 weight ratio, preferably 30 to jj weight ratio, and for knee water (J-), 0 to jM volume ratio, preferably θ~/,! I will be in charge of fM quantity.

100 parts by weight of this reaction mixture is generally 3! ~90 parts by weight of polyisocyanate, preferably 3j-60 parts by weight, are reacted, although larger amounts of incyanate can be used.

Although it is preferred that the foamable composition be prepared in the absence of a solvent, it can be prepared in a solvent. I am particularly interested in foam, and the stiffness is about 0 to 90 g.
kg777? ”, preferably ioo~ot00ky/
As a particularly balanced combination between the low density desired for insulation properties and the mass per unit volume required for foaming action when exposed to flame, the present invention Obtained by approximately /, !0 ~ Otsu 00 kl/
An example is 7 ohms with a density of m8.

Although various reaction components can be combined one by one,
a component reactive with the polyisocyanate (component/), optionally after heating for a period of time, giving a liquid reaction component containing all the necessary components apart from the polyisocyanate; 2.
It is most convenient to prepare a premix of 3, II and, optionally, j. In this way, the foamable compositions of the invention can be formulated in the form of, or produced from, two-part mixtures. Machines commonly encountered in polyurethane technology can be used for that purpose.

Premixtures of components as well as incyanates and even other components, such as urea, urea condensates, formaldehyde condensates, phenolic resins, phosphates, amines? acid esters such as tricresyl phosphate or dibutyl cresol phosphate, aluminum oxide hydrate, glass powders, blowing agents, vermiculite, solid or hollow but russet beads or other silicate beads and other substances that change the combustion behavior. It is also quite possible to add additives.

Advantageously, in order to produce the optionally foamed foamable compositions of the present invention, other types of additives than those commonly encountered in the catalyst or foam chemistry for the foam-forming reaction, such as gaseous or Although it is not necessary to use low-boiling blowing agents or blowing gas products, additional auxiliaries such as emulsifiers, dispersants, colorants, preservatives,
Hydrolytic inhibitors, perfumes or other additives can of course also be taken into consideration for use as components of the formulation in individual cases. The use of catalysts promoting the formation of carboimide groups, of the known types such as phospholine oxides, such as /-methyl-/-oxyphosphorine, provides foamable compositions with improved resistance to hydrolysis. Roar things.

Additionally, additives of the type that can assist in increasing foaming when exposed to flame can also be used in the formulation of the foamable compositions of the present invention. Such additives may be one such as aliphatic and, more particularly, aromatic hydroxyl carboxylic acids, such as polycylic acid or p-hydroxybenzoic acid, or those which release water, carbohydrates, nitrogen or carbon dioxide at elevated temperatures. substances such as triazoles,
Azocica # g y 7 mido, sulfohydrasodo or urea-dical? 7 acid anhydrides.

For example, compaction or shaping and dulling, cutting!
From the foamable composition of the present invention by melting, about
It is possible to foam at temperatures of 200-30°C and thereby produce moldings that prevent the spread of flames, ie suitable for use as sealing elements, safety devices and firebreaks. For example, foamable compositions and stones and/or foamed particles 1 such as foamed clay, foamed glass, vermiculite, perlite and 7.
Furthermore, it is possible to make a type of concrete from foamed beads, such as foamed beads based on polystyrene, and use it for filling gaps and sealing cable openings. Cable openings can be sealed.

Beams and panels made of metal, e.g. on doors, roof beams, on brickwork, on plastic, in almost all thicknesses, whether in cable insulation or foam panels It is also of interest to produce optionally reinforced coatings. Applying colting to loaded panels or supporting structures, e.g. foamed metal panels, metal panels, board-to-board, wood-ceramic or plastic straddles By doing so, flame-retardant flannel or wall elements can be easily produced.

Foamable compositions are also of interest in the production of antireflective coatings or noise insulation elements.

The foamable compositions can also be used to paint the interior of fire doors, which foam in the event of a fire and form a layer with an insulating effect. The composition can also be used to make doors and other seals that foam and close gaps in front in case of fire. For example, the sealing profile of an elastic material can be coated or lined with the optionally powdered foamable composition of the present invention and a fire-resistant sealing can thus be obtained. Chimney 1 vents and air conditioning pipes and inlet/outlet opening obstructions that, by suitable placement, will retard or prevent further gas from escaping when heated to about -00 to ≠00 °C. Can be installed inside equipment. Arrangements of this type include, for example, a number of closely spaced parallel plates, a sieve coated with a foamable composition and a perforated screen I.
A pipe section is loosely packed with granules of an effervescent composition. The optionally foamed foamable composition can also be used as a filter element for gases, which closes if the temperature rises too much.

For example, shaped articles or/stages easily obtained from foamable compositions or! Even granules with different particle sizes in stages can be heated to temperatures above 200°C, preferably!
! A temperature of 0 to /♂θ0°C, and more preferably #i,
Foaming can be achieved by heating to a temperature of 2!0-00°C.

Foaming can be carried out by free foaming or in a closed or open mold; when carried out in a mold, it is best to have ports in the mold to allow air and water vapor to escape. It's convenient. In this way the fireproof form,
So-called carbonized foams are formed by treatment with superheated steam or hot air or other hot gases, by microwave or radio frequency waves, by heat conduction in air or by liquid or metal baths, by radiant heat. Heating can be carried out.

The foamable compositions of the present invention can also be prepared, for example, by mffling expanded clay particles, pouring them into a mold and heating them in the mold, thereby embedding them in a carbonizable foam. It can also be applied and foamed onto a support material by forming a mass of foamed clay. A correspondingly coated wood neck or iron plate can be treated at about 300°C to form an fc composite foam flat panel with a 7 ohm surface treated with another plate of wood or iron. can.

The foamable compositions of the invention can also be prepared by introducing a suitable amount of the reaction mixture or foam into the foam of a cold, cold or warm brick, e.g. a cable duct). Can be used to fill spaces in clay bricks and other building materials.

The foamable composition of the invention in the form of a complete tube with half-tube dimensions is also suitable for insulating tubes or cables.

In this regard, it is of interest that insulation can also be accomplished in situ by coating the tube or article to be insulated with a reaction mixture and optionally foaming the reaction mixture thereon.

Flame retardant housings, parts thereof, containers and covers or other molded articles can also be made from rigid foam compositions.

The preparation and processing of the reaction mixture leading to the foamable composition can be carried out either continuously or batchwise. Each component is f
In each case, fc is combined in the form of a mixture. Preferably, all reaction components except the isocyanate are mixed so that a two-component process can be carried out, e.g. in a conventional small vessel equipped with a mechanical stirring device, in a stirring device or a jet mixing head, or in a polyurethane chemical. It is combined in a target mixer of the type also known from. The foaming reaction is carried out by free foaming, or without or under pressure, cooled, cold or with zero force! It can be carried out in a lA type.

[Examples and effects of the invention]

EXAMPLES The examples below are intended to illustrate the present invention and are not intended to limit it in any way. Unless otherwise indicated, quantities are expressed as a percentage and/or as a percentage.

The following series of tests is intended to illustrate the relationship between formulation and properties of the foamable compositions obtained according to the invention.

The next reaction component, namely polyisocyanate (1), is obtained by phosdanization of an aniline-formaldehyde condensate, and contains about 4 J of trinuclear diisocyanate and about 3 J of polynuclear isocyanate.
%, commercially available. Standard industrial polyisocyanate isomer mixture, highly branched polyester (3) with OH number -
2 tons; acid value 3. ．． 2Nia Viscosity at 5℃ 9.20e
Neopentyl glycol with P and functionalities about 7% by weight, adipic acid/wt%, R-taerythritol about 9'xis, glycerol about t'figs'amount'l
y and ethylene glycol, as polyesters, adducts of ethylene oxide and glycerol (OH number, 2si) prepared by alkaline catalysis according to the prior art; phosphorus-containing condensation products (
2) is referred to as p-diol (,2) in this specification 1. Industrial quality (C2H50)2PO・CH2N(
C2H40H) 2° As melamine phosphate, an adduct of 0.75 mol of orthophosphoric acid and 1 mol of melamine, obtained by combining the components in water and drying the reaction mixture at 130° C., was used. .

(Left below) Composition of mixture Melamine (4'), parts / (X) 30 - - -
-Water (1st part) Q/ -OJ OJ O, 30J pa?
Riester (3) Part 1 Gu3 30,! tO,8-,
2 Polyether (3) 9 parts 7 - - ~ - G 3
p-diol (,2), parts 100100 100 1
00 100/(1) Melamine phosphate e) 1 part -70100100100/(1) This mixture is stirred at room temperature with 7.20 parts of polyincyanate (1). The reaction mixture thus obtained starts foaming and hardens about 30 seconds after the start of mixing, and the reaction ends about 5 minutes later. The 7 ohms produced in Examples 3 and 3 have a density of about 17 m, and in Example 3 produce a stiff material with a density of about /00 ky/m.

In order to test the behavior of these solid 7 ohms obtained when exposed to a flame, a cube of - side with length /, J' cm was placed in the flame of a Bunsen burner on a metal grate. The sample is exposed from the side.

In both cases, the foam does not burn, but instead foams violently (volume increases to gooct) and carbonizes. Flame application test
When the Bunsen burner was briefly removed during the test), the flame went out immediately in both cases. In Examples/--B, when exposed to flame, the cubic sample foams and expands to several times its original volume (foaming effect).

Apart from the fact that when the amount of melamine phosphate used is half, as in Example 2-B, the foamed foamable composition tends to slightly afterburn (j~/! seconds). It has a density reduced by approximately 2 parts % for essentially the same combustion characteristics.

In order to test the foamability, a coin-shaped disk (diameter 2.3 cm - thickness 0.6 cm) was cut out from the pellets obtained in Examples/--B, and the inner diameter was 2.4 cm.
Then, the brass tube with a disc of the material at the lower end was placed vertically into a chamber preheated to 10°C. and leave in it for 30 minutes. A test was then performed to determine the height that the expandable foam rose within the tube, and the following heights were measured:

Example number Upper height/Meoσ, 2 ggm 3 7.0tyn 7. /cm! /:,, 9 cm 3 g on In order to test the fluidity of the foamable shrine t1, the above test cube was placed on a smooth steel plate heated to about 700°C and tilted at an angle of 10:'. I placed it.

In the case of fluid effervescent materials, the test cubes begin to fall off due to melting. The material obtained by implementation f113 foams without dropping the foamable foam formed at the interface between the hot zone and the cold material, and 1!
After i3, it remains in its original position exposed to the flame on the resulting insulating foam 7 ohm.

This material does not begin to burn during exposure to flame.

In Example 3, one reaction mixture was prepared.

It is applied through a nozzle onto a moving belt in the form of a strand with an n diameter of approximately 7.3σ. This If4 is foamed onto a strand to form a near-infinite profile of foamed foamable composition with a semi-circular cross-section, which can be cut and used as a foamed gap sealing profile.

Example 7 The procedure is similar to Example 7, except that non-anodiamide fine powder is used instead of melamine. Example/
Rigid expandable foams with similar mechanical properties are used. In the flame application test, it is distinguished from the foam obtained in Example/by the fact that the increase in volume is more rapid. The same phenomenon is observed when, as in Example 1, a mixture of equal parts by weight of melamine phosphate and dicyanodiamide is used instead of melamine phosphate.

Example g Replacing the polyinsyanate (1) used in Example 3 with a similarly obtained industrially produced isocyanate (1) having a polynuclear component of about 10, as opposed to about 3j. The -C1 procedure is similar to Example 3, except that. Unlike the composition obtained in Example 3, the composition was different from the composition obtained in Example 3 in that the foamed, hard, and foamable hydroxide was obtained, and its density was reduced by about 20 orders of magnitude to about 20 kq/m3. are doing. Flame overflow C1 (in our experiments, there was no after-combustion, and a pulsation of over 300 flames was observed).

Example? A clay tile with a thickness of about 1/cm is cut with a milling cutter to form a total length of about 10α and a W of rlJ/cm.

The tile is then placed flat on the polyethylene film,
The reaction mixture of Example- is then poured into the groove. After curing, the foamable composition is left overlapping on the tile surface with a width of about 2 ohms, i.e. 7 ohms introduced into the grooves are spread across a roughly T-shaped profile. ?
At Roku, Fumishi et al. cut out the material that had protruded from the grooves on the surface of the tile. Next, we processed the mail in this way.

The effervescent composition that fills the base of the tile, i.e., the base, creates a gap between the outer details of the non-bright flame of natural gas and the inner conical blue flame.
] Place it on top of the Bunsen burner so that it is placed in the middle of the hole. When the flame application test is performed in this position,
After 1 minute of 90 minutes, the flame stopped burning due to filling of the groove.

Example 10 One side of the foamable old material produced according to the formulations of Examples 3 and 3 and ! ; A cube with a length of cm was cut out. Some of the cubes are placed in /l of water and stored under the surface of the water for g days by means of a screen.

The cubic samples are then dried and subjected to a flame application test in the same manner as in Examples/~6. Compared to control cube samples that were not stored in water, this flame application test left the foaming properties completely intact.

Moreover, the foaming behavior did not deteriorate (foam height 7
crn/type 3).

EXAMPLE // The reaction mixture prepared according to example j is introduced into a wax-impregnated circular button beaker-like mold and foamed therein. After about 70 minutes, the conical molded product is removed from the mold. The molded article is used as a flame spread resistant plug for a lightweight through-wall or generally round hole at the end of a tube by pushing it into the hole. This type of opening is thus side-chained against the ingress of smoke gases.

Example/2 A reaction mixture is prepared in the same manner as in Example 3, except that no water is used.

When such a reaction mixture is sprayed onto a clean steel surface before curing, it hardens to form a water-distributing coating characterized by excellent adhesion and foaming properties, resulting in steel is protected from the advance of flame.

The vertical and durable foamable composition can also be used as a component for producing pods for holding lines or tubes. When applied to wire wraps, the composition provides effective protection against flame penetration.

This type of sheath (sleeve) is an example! . If the part is removed early, it may be subjected to further forming operations, such as bending or compression using a heated or cold mandrel, or conical expansion, before it is finally cured. can be administered.

The mixture of Example 3 or/2 can be used to produce, for example, a tubular sleeve with an outer noyakut of half-tubular sheet steel. These tubular sleeves
When fastened to a sleeve of a tube of thermoplastic material, for example, this tube is compressed by the inlamellar sense of the contents of the sleeve and is thereby protected from the advance of fire. This foamable material can eventually completely fill and seal the thermoplastic tube exposed to the fire.

Claims (7)

[Claims] (1) /,yJ? Liisocyanate 3j-ta OX floor. 2. Condensation of aliphatic, cycloaliphatic, aromatic, arasophatic or heterocyclic primary or primary monoamines and/or polyamines, cargenyl compounds and noalkyl phosphites, optionally containing hydroxyl groups. and, optionally, a phosphorus-containing condensation product containing at least two hydroxyl groups obtained by subsequent alkoxyΦsylation, 20-7! Weight staff. 3. C2-C1o polycarboxylic acids can be classified into three groups: a) containing more than 3 hydroxyl groups, and! O
A hydroxyl compound having a molecular weight of θ or less; b) A hydroxyl compound containing 3 hydroxyl groups and having a molecular weight of /jθ or less. c) hydroxyl compounds containing two hydroxyl groups and having a molecular weight of /10 or less, obtained by reacting with at least two glazes of polyols selected from one different group. Number of OH/1lt0
Hydroxyl-containing polyester with ~300, 2~
30 by weight, where the polyol of the above polyols is a
) group and obtained by adding an alkylene oxide consisting of ethylene oxide to a low molecular weight starting material. Optionally, polyethers with an average OH number of 20 to 300 are used, by reacting with 100 parts by weight of a mixture consisting of 20 to 75% by weight of melamine and/or melamine derivatives and 0-1% by weight of water. The resulting optionally porous foamable composition. (2) The foamable composition according to claim (1), characterized in that the polyisocyanate used is a polyisocyanate of the type obtained by phosdanizing an aniline-formaldehyde condensate. (3) A foamable composition according to claim (1) or (2), characterized in that the condensation product containing at least one hydroxyl group used corresponds to the following formula: thing. (RO)2PO-CH,, -N-(CHX-CHX-O
H) In the formula 2, R is a C1-C8 alkyl group or C, -C
8 represents a hydroxyalkyl group, and X=hydrogen or a methyl group. (4) Any one of claims (1) to (3), characterized in that highly branched polyesters of adipic acid, pentaerythritol, glycerol and ethylene glycol are used as the polyester. The foamable composition described in . (5) The foamable composition according to any one of claims (1) to (4), characterized in that melamine phosphate is used as the melamine derivative. (6) Using the foamable composition according to any one of claims (1) to (5), foamable cavity filling materials, gap sealing materials, sheets, semi-finished products and Method of manufacturing coatings. (7) Obtained by reaction in a mold or by subsequent shaping of a fully reacted reaction mixture. A method for producing a molded article having 1 foamability using the foamable composition according to any one of claims (1) to (5).